Evaluation of extraction chromatography resins for rapid actinide analysis

217 Pages·2016·4.16 MB·English

by  Julie Marisa Gostic

UNLV Theses, Dissertations, Professional Papers, and Capstones
2009
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Julie Marisa Gostic
University of Nevada Las Vegas
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EVALUATION OF EXTRACTION CHROMATOGRAPHY RESINS FOR RAPID
ACTINIDE ANALYSIS

By

Julie Marisa Gostic

Bachelor of Arts
College of Charleston
2000

Masters of Science
University of Massachusetts, Lowell
2004

A dissertation submitted in partial fulfillment of
the requirements for the

Doctor of Philosophy Degree in Radiochemistry
Department of Chemistry
College of Science

Graduate College
University of Nevada, Las Vegas
December 2009
THE GRADUATE COLLEGE

We recommend that the dissertation prepared under our supervision by

Julie Marisa Gostic

entitled

Evaluation of Extraction Chromatography Resins for Rapid
Actinide Analysis

be accepted in partial fulfillment of the requirements for the degree of

Doctor of Philosophy
Radiochemistry

Kenneth Czerwinski, Committee Chair

Kenton Moody, Committee Member

Gary Cerefice, Committee Member

Ralf Sudowe, Graduate Faculty Representative

Ronald Smith, Ph. D., Vice President for Research and Graduate Studies
and Dean of the Graduate College

December 2009

ii
ABSTRACT
Evaluation of Extraction Chromatography Resins for Rapid Actinide
Analysis

by
Julie M. Gostic
Dr. Kenneth R. Czerwinski, Examination Committee Chair
Professor of Chemistry
Chair of the Department of Radiochemistry
University of Nevada, Las Vegas
In this work, physical and chemical parameters associated with extraction
chromatography separation procedures were investigated for rapid actinide
analysis. A vacuum box system was designed in-house and was characterized in
terms of flow rate reproducibility, matrix effects on flow rate for sequential elution,
and actinide separation efficiency using different types of resin (TEVA, DGA and
TRU). Results indicated that the columnar kinetics of the resins were sufficiently
rapid to run high purity samples through the unit over a wide range of flow rates
for all resin types. Single matrix interferences at a metal ion ratio of 1:106 relative
to the actinide of interest affected separation efficiency with some resins and a
flow rate dependency was observed. After parameter optimization, the system
was used to isolate Pu for isotopic analysis from dissolved particles from a
nuclear warhead that was destroyed in a fire 50 years ago. Isotopic analysis was
obtained by a combination of radiometric and mass-based methods using cerium
fluoride (CeF ) micro-precipitation for sample preparation. The results of these
3
experiments were compared to historical record surrounding the source of the
particles.
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ACKNOWLEDGEMENTS
I would like to take this opportunity to express my sincerest gratitude to those
individuals that helped me reach this milestone in my educational career. First, I
would like to thank my thesis advisor, Ken Czerwinski for having the foresight
and tenacity to build a multi-disciplinary radiochemistry program at UNLV. I have
benefited from his hard work and dedication to the program and would like to
thank him in particular for his efforts. I would also like to thank the members of
my thesis committee for their patience and support throughout my research and
writing. In particular, I would like to thank Ken Moody for his thoughtful
commentary and hours of time spent reviewing this body of work. Gary Cerefice
and Ralf Sudowe have also been very influential in my professional growth and
development and I thank them for their guidance and support throughout my
graduate career at UNLV.
I could not have accomplished this without the love and support of friends and
family. To my husband, I am eternally grateful for your unwavering support and
willingness to complete our PhDs together. I would like to dedicate this work to
those on whose shoulders I stand, Linda Jones, Mike Ryan, Nancy Carder, Sy
Baron, David Borsook, Jeanette Cohan, Lino Becerra, Clay French, Mark Tries,
Jim Eagan, and Dave Medich.

iv
TABLE OF CONTENTS
ABSTRACT .......................................................................................................... iii

ACKNOWLEDGEMENTS .....................................................................................iv

LIST OF TABLES ............................................................................................... viii

LIST OF FIGURES ............................................................................................... x

CHAPTER 1 INTRODUCTION .................................................................. 1
1.1 Background ............................................................................................... 1
1.2 Bulk Sample Processing Through Automation .......................................... 3
1.3 Method Selection ...................................................................................... 3
1.4 Source Preparation and Analysis .............................................................. 5
1.5 Thesis Organization .................................................................................. 6

CHAPTER 2 INSTRUMENTATION AND METHODS................................ 9
2.1 Introduction ............................................................................................... 9
2.2 Chemical Separations ............................................................................... 9
2.3 Radionuclide Standards .......................................................................... 12
2.3.1 Americium ................................................................................... 12
2.3.2 Plutonium .................................................................................... 12
2.4 Cerium Fluoride Precipitation Sample Preparation ................................. 17
2.5 Alpha Spectrometry ................................................................................. 18
2.5.1 Detector Calibration .................................................................... 19
2.5.2 Data Analysis .............................................................................. 23
2.6 Gamma Spectrometry ............................................................................. 23
2.6.1 Detector Calibration .................................................................... 24
2.6.2 Data Analysis .............................................................................. 26
2.7 Liquid Scintillation Counting .................................................................... 27
2.7.1 LSC Sample Preparation ............................................................ 27
2.7.2 LSC Counting Method ................................................................. 28
2.7.3 LSC Efficiency Calibration: Mineral Acid Affects ......................... 29
2.7.4 LSC Analysis .............................................................................. 33
2.8 Inductively Coupled Plasma-Atomic Emission Spectrometry .................. 33
2.8.1 Sample Preparation .................................................................... 34
2.8.2 Instrument Settings ..................................................................... 35
2.8.3 Analyte Analysis ......................................................................... 37
2.9 Inductively Coupled Mass Spectrometry ................................................. 39
2.9.1 Sample Preparation .................................................................... 40
2.9.2 Instrument Settings ..................................................................... 40
2.9.3 Analyte Parameters .................................................................... 41
2.9.4 Analyte Interferences .................................................................. 42

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CHAPTER 3 EXTRACTION CHROMATOGRAPHY PERFORMANCE
AMERICIUM SEPARATIONS ............................................ 43
3.1 Abstract ................................................................................................... 43
3.2 Introduction ............................................................................................. 44
3.3 Materials and Methods ............................................................................ 47
3.3.1 Vacuum Extraction System ......................................................... 47
3.3.2 Reagents .................................................................................... 48
3.3.3 Radionuclide Standards .............................................................. 49
3.3.4 Flow Rate Characterization ......................................................... 50
3.3.5 Americium Separation ................................................................. 50
3.3.6 Elemental Matrix Interference Effects ......................................... 51
3.4 Results and Discussions ......................................................................... 53
3.4.1 Vacuum Extraction System Characterization .............................. 53
3.4.2 Effects of Flow Rate on Americium Extractions .......................... 60
3.4.3 Sorption of Elemental Matrix Interferences ................................. 62
3.4.4 TRU Resin Capacity of Selected Metal Ions ............................... 65
3.4.5 DGA Resin Capacity for Selected Metal Ions ............................. 67
3.4.6 Effects of Elemental Matrix Interferences on 241Am Separation
Efficiency .................................................................................... 69
3.5 Concluding Remarks ............................................................................... 72

CHAPTER 4 EXTRACTION CHROMATOGRAPHY PERFORMANCE -
PLUTONIUM SEPARATIONS ............................................ 73
4.1 Abstract ................................................................................................... 73
4.2 Introduction ............................................................................................. 73
4.3 Materials and Methods ............................................................................ 77
4.3.1 Vacuum Extraction System ......................................................... 77
4.3.2 Reagents .................................................................................... 77
4.3.3 Radionuclide Standards .............................................................. 78
4.3.4 Flow Rate Characterization ......................................................... 79
4.3.5 Plutonium Separation .................................................................. 79
4.3.6 Elemental Matrix Interference Effects ......................................... 81
4.4 Results and Discussions ......................................................................... 83
4.4.1 Vacuum Extraction System Characterization .............................. 83
4.4.2 Effects of Flow Rate on Plutonium Extractions ........................... 84
4.4.3 Optimization of Redox Reagent Addition .................................... 86
4.4.4 Sorption of Elemental Matrix Interferences ................................. 88
4.4.5 Effects of Elemental Matrix Interferences on 239Pu Separation
Efficiency ............................................................................................. 90
4.5 Concluding Remarks ............................................................................... 94

CHAPTER 5 HOT PARTICLE DISSOLUTION AND PLUTONIUM
ISOTOPIC ANALYSIS ........................................................ 96
5.1 Abstract ................................................................................................... 96
5.2 Introduction ............................................................................................. 96
5.3 Materials and Methods .......................................................................... 100
vi
5.3.1 Reagents .................................................................................. 100
5.3.2 Particle Dissolution ................................................................... 101
5.3.3 Chemical Separations ............................................................... 102
5.3.4 Sample Preparation for Plutonium Isotopic Analysis ................ 104
5.3.5 Plutonium Isotopic Analysis – Gamma and Alpha Spectrometry
........................................................................................................... 105
5.3.6 Elemental Analysis .................................................................... 110
5.4 Results and Discussion ......................................................................... 112
5.4.1 Plutonium Isotopic Composition – Historical Record................. 112
5.4.2 Particle Dissolution ................................................................... 113
5.4.3 Bulk Activity Ratios ................................................................... 117
5.4.4 Chemical Separations ............................................................... 118
5.5 Plutonium Isotopic Composition ............................................................ 121
5.5.1 Relative Abundance of 240Pu .................................................... 121
5.5.2 Relative Abundance of 238Pu .................................................... 123
5.5.3 Relative Abundance of 241Pu .................................................... 123
5.5.4 Elemental Analysis .................................................................... 126
5.6 Concluding Remarks ............................................................................. 129

CHAPTER 6 PLUTONIUM ISOTOPIC STANDARD DEVELOPMENT FOR
GAMMA, ALPHA AND MASS SPECTROMETRY ............ 132
6.1 Abstract ................................................................................................. 132
6.2 Introduction ........................................................................................... 133
6.3 Materials and Methods .......................................................................... 136
6.3.1 Reagents .................................................................................. 136
6.3.2 Radionuclide Standard .............................................................. 136
6.3.3 Sample Preparation .................................................................. 139
6.3.4 Cerium Fluoride Co-Precipitation .............................................. 141
6.3.5 Analysis by ICP-MS .................................................................. 142
6.3.6 Plutonium Isotopic Analysis – Gamma Spectrometry ............... 149
6.3.7 Plutonium Isotopic Analysis – Alpha Spectrometry ................... 151
6.4 Results and Discussion ......................................................................... 154
6.4.1 Alpha Analysis .......................................................................... 154
6.4.2 Gamma Analysis ....................................................................... 161
6.4.3 Mass Analysis – Aqueous Solution ........................................... 164
6.4.4 Mass Analysis – CeF Filter ...................................................... 169
3
6.5 Concluding Remarks ............................................................................. 178

CHAPTER 7 CONCLUDING REMARKS AND REFLECTIONS ON
FUTURE RESEARCH ...................................................... 179

BIBLIOGRAPHY ............................................................................................... 187

VITA ................................................................................................................. 202

vii
LIST OF TABLES
Table 1 Extraction chromatography resins used for actinide separations ..... 10
Table 2 Plutonium isotopic content of aqueous standard (Isotope Products,
1198-16-1) ....................................................................................... 14
Table 3 Efficiency calibration source information .......................................... 20
Table 4 Alpha energy ROIs used for data analysis ....................................... 23
Table 5 Photon energy and radiative yield information used for determining
Pu isotopic ratios and Am separation efficiency by gamma
spectrometry. ................................................................................... 25
Table 6 ICP-AES calibration standard preparation ....................................... 36
Table 7 Matrix ion photon wavelengths used to determine signal intensity on
the ICP-AES. ................................................................................... 38
Table 8 Plutonium m/z ratios used for ICP-MS analysis for both aqueous and
CeF co-precipitated samples. ......................................................... 41
3
Table 9 Method elution matrices used for 241Am separation. ........................ 51
Table 10 Matrix ion photon wavelengths used to determine signal intensity on
the ICP-AES. ................................................................................... 53
Table 11 241Am separation efficiency for TRU and DGA resins in the presence
of selected ions. ............................................................................... 69
Table 12 Method elution matrices used for 239Pu separation on TEVA resin .. 80
Table 13 Matrix ion photon wavelengths used to determine signal intensity on
the ICP-AES. ................................................................................... 82
Table 14 Redox reagent aging effects on Pu efficiency on TEVA resin. ......... 87
Table 15 Plutonium activity percent recovered in each collected method
fraction determined by LSC counting in the presence of selected ions
......................................................................................................... 92
Table 16 Plutonium isotopic composition of the nuclear missile in 1958. ....... 99
Table 17 Detection efficiency for selected photons using the broad energy
germanium (BEGe) spectrometry system. ..................................... 108
Table 18 Photon wavelengths used to determine signal intensity for the ICP-
AES ............................................................................................... 111
Table 19 Activity recovered from hot particle dissolutions vs. estimated activity
from non-destructive gamma spectrometry analysis. ..................... 115
Table 20 Sample geometry dependence on high resolution gamma
spectrometry detection efficiency. .................................................. 116
Table 21 Decay corrected plutonium isotopic standard information. ............ 138
Table 22 Total activity and mass values based on 239Pu for each sample
solution within a set of 7. Four sets of aqueous solutions were
prepared, 2 for CeF and 2 for ICP-MS. ......................................... 140
3
Table 23 Plutonium m/z ratios used for ICP-MS analysis for both aqueous and
CeF co-precipitated samples. ....................................................... 143
3
Table 24 Operating parameters for the CETAC laser ablation system, LSX500
and ELAN ICP-MS. ........................................................................ 148
viii
Table 25 Detection efficiency for selected photons emitted in the decays of the
indicated Pu isotopes using the broad energy germanium (BEGe)
spectrometry system. ..................................................................... 150
Table 26 Alpha spectrometry isotopic analysis prior to and after 241Am
separation. ..................................................................................... 155
Table 27 Gamma spectrometry isotopic analysis prior to and after 241Am
separation. ..................................................................................... 163
Table 28 Aqueous ICP-MS detection limits for the Pu isotopic m/z ratios. ... 165

ix